Polymers and their use

ABSTRACT

A substituted polysaccharide comprising β 1-4  linkages having covalently bonded on the polysaccharide moiety thereof, at least one deposition enhancing group which undergoes a chemical change in water at a use temperature to increase the affinity of the substituted polysaccharide to a substrate, the substituted polysaccharide further comprising one or more independently selected silicone chains.

TECHNICAL FIELD

[0001] The present invention relates to a substituted polysaccharide ofthe kind comprising a benefit agent and a deposition aid for depositionof the benefit agent onto a substrate. It further relates to a method ofdepositing a benefit agent from solution or dispersion, onto asubstrate.

BACKGROUND OF THE INVENTION

[0002] The deposition of a benefit agent onto a substrate, such as afabric, is well known in the art. In laundry applications typical“benefit agents” include fabric softeners and conditioners, soil releasepolymers, sunscreens; and the like. Deposition of a benefit agent isused, for example, in fabric treatment processes such as fabricsoftening to impart desirable properties to the fabric substrate.

[0003] Conventionally, the deposition of the benefit agent has had torely upon the attractive forces between the oppositely charged substrateand the benefit agent. Typically this requires the addition of benefitagents during the rinsing step of a treatment process so as to avoidadverse effects from other charged chemical species present in thetreatment compositions. For example, cationic fabric conditioners areincompatible with anionic surfactants in laundry washing compositions.

[0004] Such adverse charge considerations can place severe limitationsupon the inclusion of benefit agents in compositions where an activecomponent thereof is of an opposite charge to that of the benefit agent.For example, cotton is negatively charged and thus requires a positivelycharged benefit agent in order for the benefit agent to be substantiveto the cotton, i.e. to have an affinity for the cotton so as to absorbonto it.

[0005] Often the substantivity of the benefit agent is reduced and/orthe deposition rate of the material is reduced because of the presenceof incompatible charged species in the compositions. However, in recenttimes, it has been proposed to deliver a benefit agent in a form wherebyit is substituted onto another chemical moiety which increases itsaffinity for the substrate in question.

PRIOR ART

[0006] WO-A-98/00500 discloses detergent compositions comprising apeptide or protein deposition aid having a high affinity for fibres or asurface, and a benefit agent attached/adsorbed to the deposition aid.However, this deposition aid does not change chemically such as toincrease its affinity for the substrate during the treatment process.

[0007] GB-A-1 031 484 discloses stable aqueous dispersions of elasticcopolymers which can be converted to cross-linked polymers by the actionof heat or acid. They can be used to produce films or covering layers.However, none of the compounds has a benefit agent attached to thedeposition enhancing part. There is no disclosure of using thesematerials in methods of laundry or fabric care.

[0008] U.S. Pat. No. 5,730,760 discloses a process of fabric washing inwhich a dye redeposition inhibiting agent is used. The dye redepositioninhibiting polymer used is of a specific type, being produced bypolymerising, for example, vinylester monomers. There is not any mentionof materials having any surface substantive properties nor is there adescription of any reaction by which such surface substantive propertiesincrease during use.

[0009] WO-A-92/13114 discloses hair fixative polymers which form a filmafter application. The polymers are fundamentally different from thoseof the present invention in that they do not comprise a deposition partattached to a benefit agent. The polymeric material has no particularaffinity for hair—it is just applied onto it. There is certainly nomention of a reaction which increases the affinity. Any reaction whichoccurs leads to the cross-linking of polymer and the formation of film.It is not disclosed that the polymers should be water-soluble ofdispersible—they are normally dissolved in an inert carrier such asalcohol.

[0010] WO-A-95/35087 discloses a hair fixative amphoteric polymercomposition. It is insoluble in water but can be solubilised by use ofneutralisers or solubilising alcohol/water mixtures. The polymers do notto undergo any reaction which increases their affinity for hair. Thereis no benefit agent attached to the polymer.

[0011] WO-A-98/29528 discloses cellulose ethers in which somesubstituents are (poly)alkoxylated, analogues of the latter in which the(poly)alkoxylated groups are terminated with a cationic moiety in theform of a quaternary ammonium group, and cellulose ethers in which somesubstituents are carboxylic acids in the salt form (i.e. the materialsare essentially carboxymethylcellulose variants). None of thesesubstituents in any variant is of a kind which would undergo a chemicalchange to enhance fabric affinity.

[0012] WO-A-99/14245 discloses laundry detergent compositions containingcellulosic based polymers to provide appearance and integrity benefitsto fabrics. These polymers are cellulosic polymers in which thesaccharide rings have pendant oxygen atoms to which substituents ‘R’ arebonded, i.e. they are attached to the rings via an ether linkage. Thegroups ‘R’ can be hydrogen, lower alkyl or alkylene linkages terminatedby carboxylic acid, ester or amide groups. Optionally, up to fivealkyleneoxy groups may be interspersed between the groups are therespective oxygen atom. None of the pendant groups is a benefit agentgroup. However, at least some of these groups may undergo a chemicalchange such as hydrolysis, in the wash liquor. However no such changewould result in an increased affinity for the fabric. On the contrary,because the “ester” group is configured with the carbonyl group closerto the polysaccharide than the oxygen atom (i.e. esters of carboxyalkylgroups), any hydrolysis will result in free acid substituents which willactually result in an increase in solubility and therefore, a decreasein affinity for the fabric.

[0013] WO-A-99/14295 discloses structures analogous to those describedin WO-A-99/14245 but in one alternative, the substituents ‘R’ togetherwith the oxygen on the saccharide ring, constitute pendant half-estersof certain dicarboxylic acids. A single example of such a material isgiven. Again, no pendant group is a benefit agent group. However, thedicarboxylic acid half-esters would tend to hydrolyse in the wash liquorand thereby increase affinity of the material for a cotton fabric.However, first, this mechanism of action or behaviour is not mentioned.Second, the hydrolysis rate of such dicarboxylic acids half esters isnot as great as that of esters of monocarboxylic acids (which are notdisclosed or claimed in WO-A-99/14295). Third, the degree ofsubstitution for this variant is specified as being from 0.001 to 0.1.This is so low as to make the enhancement of fabric affinity too low tobe worthwhile for this mechanism of action. Fourth, the structuresdescribed and claimed insofar as they have such half ester substituents,must also have substituents of the type which are carboxyalkyl groups oresters thereof, i.e. of the type also described in WO-A-99/14245. In thelatter (ester) case, these would hydrolyse to the free acid form. Thedegree of substitution of the latter (0.2 to 2) is considerably higherthan for the half-ester groups and the resultant increase in solubilitywould easily negate any enhanced affinity for the fabric by hydrolysisof the half-ester groups.

[0014] WO-A-00/1 8861 provides a water-soluble or water-dispersiblematerial for deposition onto a substrate during a treatment process,wherein the material comprises:

[0015] (i) a deposition enhancing part having a polymeric backbone; and

[0016] (ii) a benefit agent group attached to the deposition enhancingpart by a hydrolytically stable bond;

[0017] such that the material undergoes during the treatment process, achemical change which does not involve the hydrolytically stable bondand by which change the affinity of the material onto the substrate isincreased. The preferred materials are substituted polysaccharides.

[0018] WO-A-00/18861 mentions as possible benefit groups, lubricants,ironing aids and fabric softeners. However, it is known that siliconematerials are especially useful agents for delivering this kind ofbenefit. Up to now, there has been no specific teaching of how todeliver a silicone to a cotton substrate by use of a polysaccharide. Thepresent invention is aimed at solving this problem.

DEFINITION OF THE INVENTION

[0019] A first aspect of the present invention provides a substitutedpolysaccharide comprising β₁₋₄ linkages having covalently bonded on thepolysaccharide moiety thereof, at least one deposition enhancing groupwhich undergoes a chemical change in water at a use temperature toincrease the affinity of the substituted polysaccharide to a substrate,the substituted polysaccharide further comprising one or moreindependently selected silicone chains.

[0020] A second aspect of the present invention provides a method fordepositing a silicone onto a substrate, the method comprising,contacting in an aqueous medium, the substrate and a substitutedpolysaccharide according to the first aspect of the invention.

[0021] A third aspect of the present invention also providescompositions comprising a material according to the first aspect of thepresent invention. In particular, such compositions preferably compriseone or more surfactants and are suitable for use in washing applicationssuch as laundry.

[0022] A further aspect of the invention provides the use of acomposition according to the third aspect to enhance the softeningbenefit of the composition on a substrate.

DETAILED DESCRIPTION OF THE INVENTION

[0023] The Substituted Polysaccharide

[0024] In the substituted polysaccharide, the silicone chain ispreferably attached to the polysaccharide by a covalent stable bond.That means that the bonding of the silicone should be sufficientlystable so as not to undergo hydrolysis in the environment of thetreatment process for the duration of that process. For example, inlaundry cleaning applications, the substituted polysaccharide should besufficiently stable so that the bond between the silicone andpolysaccharide does not undergo hydrolysis in the wash liquor, at thewash temperature, before the silicone has been deposited onto thefabric. Preferably, the bond between the silicone and the polysaccharideis such that the decay rate constant (k_(d)) of the material in anaqueous solution at 0.01 wt % of the material together with 0.1 wt % ofanionic surfactant at a temperature of 40° C. at a pH of 10.5 is suchthat k_(d)<10⁻³s⁻¹.

[0025] The substituted polysaccharide of the present invention iswater-soluble or water-dispersible in nature and comprises apolysaccharide substituted with at least one silicone attached to thepolysaccharide aid by a hydrolytically stable bond.

[0026] By water-soluble, as used herein, what is meant is that thematerial forms an isotropic solution on addition to water or anotheraqueous solution.

[0027] By water-dispersible, as used herein, what is meant is that thematerial forms a finely divided suspension on addition to water oranother aqueous solution.

[0028] By an increase in the affinity of the substituted polysaccharidefor a substrate such as a textile fabric upon a chemical change, what ismeant is that at some time during the treatment process, the amount ofmaterial that has been deposited is greater when the chemical change isoccurring or has occurred, compared to when the chemical change has notoccurred and is not occurring, or is occurring more slowly, thecomparison being made with all conditions being equal except for thatchange in the conditions which is necessary to affect the rate ofchemical change.

[0029] Deposition onto a substrate includes deposition by adsorption,co-crystallisation, entrapment and/or adhesion.

[0030] The Polysaccharide Part

[0031] The polysaccharide is preferably β₁₋₄ linked and js a cellulose,a cellulose derivative, or another β-_(1,4)-linked polysaccharide havingan affinity for cellulose, such as mannan and glucomannan.

[0032] Preferably, the polysaccharide has only β-_(1,4) linkages.Optionally, the polysaccharide has linkages in addition to the β-_(1,4)linkages, such as β-_(1,3) linkages. Thus, optionally some otherlinkages are present. Polysaccharide backbones which include somematerial which is not a saccharide ring are also within the ambit of thepresent invention (whether terminal or within the polysaccharide chain).

[0033] The polysaccharide may be straight or branched. Many naturallyoccurring polysaccharides have at least some degree of branching, or atany rate at least some saccharide rings are in the form of pendant sidegroups (which are therefore not in themselves counted in determining thedegree of substitution) on a main polysaccharide backbone.

[0034] A polysaccharide comprises a plurality of saccharide rings whichhave pendant hydroxyl groups. In the substituted polysaccharides of thepresent invention, at least some of these hydroxyl groups areindependently substituted by, or replaced with, one or more othersubstituents, at least one being a silicone chain. The “average degreeof substitution” for a given class of substituent means the averagenumber of substituents of that class per saccharide ring for thetotality of polysaccharide molecules in the sample and is determined forall saccharide rings.

[0035] The Deposition Enhancing Group

[0036] A deposition enhancing group is a group which undergoes achemical change in use, and is attached to the polysaccharide agentgroup by means of a covalent stable bond. This chemical change resultsin an increase of the affinity of the material for the substrate and isreferred to further below.

[0037] The chemical change which causes the increased substrate affinityis preferably caused by hydrolysis, perhydrolysis or bond-cleavage,optionally catalysed by an enzyme or another catalyst. Hydrolysis ofsubstituent ester-linked groups is typical. By ester linkage is meantthat the hydrogen of an —OH group has been replaced by a substituentsuch as R′—CO—, R′SO₂— etc to form a carboxylic acid ester, sulphonicacid ester (as appropriate) etc together with the remnant oxygenattached to the saccharide ring. In some cases, the group R′ may forexample contain a heteroatom, e.g. as an —NH— group attached to thecarbonyl, sulphonyl etc group, so that the linkage as a whole could beregarded as a urethane etc linkage. However, the term ester linkage isstill to be construed as encompassing these structures.

[0038] The average degree of substitution of these pendant groups whichundergo the chemical change is preferably from 0.1 to 3 (e.g. from 0.3to 3), more preferably from 0.1 to 1 (e.g. from 0.3 to 1).

[0039] The Silicone Chain(s)

[0040] As used herein the term “silicone chain” means a polysiloxane orderivative thereof. In the section “Preferred Overall Structure”hereinbelow, various preferred silicone chains are recited and these aretypically suitable, whether or not the substituted polysaccharideconforms to the preferred overall structure.

[0041] Preferred Overall Structures

[0042] Preferred substituted polysaccharides of the invention arecellulosic polymers of formula (I):

[0043] (optional β-_(1,3) and/or other linkages and/or other groupsbeing permitted in the above formula (l))wherein at least one or more—OR groups of the polymer are substituted by or replaced byindependently selected silicone chains and at least one or more R groupsare independently selected from groups of formulae:—

[0044] wherein each R¹ is independently selected from C₁₋₂₀ (preferablyC₁₋₆) alkyl, C₂₋₂₀ (preferably C₂₋₆) alkenyl (e.g. vinyl) and C₅₋₇ aryl(e.g. phenyl) any of which is optionally substituted by one or moresubstituents independently selected from C₁₋₄ alkyl, C₁₋₁₂ (preferablyC₁₋₄) alkoxy, hydroxyl, vinyl and phenyl groups;

[0045] each R² is independently selected from hydrogen and groups R¹ ashereinbefore defined;

[0046] R³ is a bond or is selected from C₁₋₄ alkylene, C₂₋₄ alkenyleneand C₅₋₇arylene (e.g. phenylene) groups, the carbon atoms in any ofthese being optionally substituted by one or more substituentsindependently selected from C₁₋₁₂ (preferably C₁₋₄) alkoxy, vinyl,hydroxyl, halo and amine groups;

[0047] each R⁴ is independently selected from hydrogen, counter cationssuch as alkali metal (preferably Na) or ½ Ca or ½ Mg, and groups R¹ ashereinbefore defined; and groups R which together with the oxygen atomforming the linkage to the respective saccharide ring forms an ester orhemi-ester group of a tricarboxylic- or higher polycarboxylic- or othercomplex acid such as citric acid, an amino acid, a synthetic amino acidanalogue or a protein;

[0048] any remaining R groups being selected from hydrogen and othersubstituents.

[0049] For the avoidance of doubt, as already mentioned, formula (I),some of the R groups may optionally have one or more structures, forexample as hereinbefore described. For example, one or more R groups maysimply be hydrogen or an alkyl group.

[0050] Preferred groups which undergo the chemical change may forexample be independently selected from one or more of acetate,propanoate, trifluroacetate, 2-(2-hydroxy-1-oxopropoxy) propanoate,lactate, glycolate, pyruvate, crotonate, isovalerate cinnamate, formate,salicylate, carbamate, methylcarbamate, benzoate, gluconate,methanesulphonate, toluene, sulphonate, groups and hemiester groups offumaric, malonic, itaconic, oxalic, maleic, succinic, tartaric,aspartic, glutamic, and malic acids.

[0051] Particularly preferred such groups are the monoacetate,hemisuccinate, and 2-(2-hydroxy-1-oxopropoxy)propanoate. The term“monoacetate” is used herein to denote those acetates with the degree ofsubstitution of 1 or less on a cellulose or other β-1,4 polysaccharidebackbone.

[0052] Cellulose esters of hydroxyacids can be obtained using the acidanhydride in acetic acid solution at 20-30° C. and in any case below 50°C. When the product has dissolved the liquid is poured into water (b.p.316,160). Tri-esters can be converted to secondary products as with thetriacetate. Glycollic and lactic ester are most common.

[0053] Cellulose glycollate may also be obtained from cellulosechloracetate (GB-A-320 842) by treating 100 parts with 32 parts of NaOHin alcohol added in small portions.

[0054] An alternative method of preparing cellulose esters consists inthe partial displacement of the acid radical in a cellulose ester bytreatment with another acid of higher ionisation constant (FR-A-702116). The ester is heated at about 100° C. with the acid which,preferably, should be a solvent for the ester. By this means celluloseacetate-oxalate, tartrate, maleate, pyruvate, salicylate andphenylglycollate have been obtained, and from cellulose tribenzoate acellulose benzoate-pyruvate. A cellulose acetate-lactate oracetate-glycollate could be made in this way also. As an examplecellulose acetate (10 g.) in dioxan (75 ml.) containing oxalic acid (10g.) is heated at 100° C. for 2 hours under reflux.

[0055] Multiple esters are prepared by variations of this process. Asimple ester of cellulose, e.g. the acetate, is dissolved in a mixtureof two (or three) organic acids, each of which has an ionisationconstant greater than that of acetic acid (1.82×10⁻⁵): With solid acidssuitable solvents such as propionic acid, dioxan and ethylene dichlorideare used. If a mixed cellulose ester is treated with an acid this shouldhave an ionisation constant greater than that of either of the acidsalready in combination.

[0056] A cellulose acetate-lactate-pyruvate is prepared from celluloseacetate, 40 per cent. acetyl (100 g.), in a bath of 125 ml. pyruvic acidand 125 ml. of 85 per cent. lactic acid by heating at 100° C. for 18hours. The product is soluble in water and is precipitated and washedwith ether-acetone. M.p. 230-250° C.

[0057] In the case of those materials having a cellulose backbone andpendant ester groups, without being bound by any particular theory orexplanation, the inventors have conjectured that the mechanism ofdeposition is as follows.

[0058] Cellulose is substantially insoluble in water. Attachment of theester groups to make a cellulose derivative causes disruption of thehydrogen bonding between rings of the cellulose chain or chains, thusincreasing water solubility or dispersibility. In the treatment liquor,the ester groups are hydrolysed, causing the cellulose derivative toincrease its affinity for the substrate, e.g. the fabric.

[0059] In the case when solubilising groups are attached to thepolysaccharide, this is typically via covalent bonding and, may bependant upon the backbone or incorporated therein. The type ofsolubilising group may alter according to where the group is positionedwith respect to the backbone.

[0060] In this specification the “n” subscript used in the generalformulae of the substituted polysaccharide is a generic reference to apolymer. Although “n” can also mean the actual (average) number ofrepeat units present in the polysaccharide, it is more meaningful torefer to “n” by the number average molecular weight.

[0061] The number average molecular weight (Mn) of the substitutedpolysaccharide part may typically be in the range of 1,000 to 200,000,for example 2,000 to 100,000, e.g. as measured using GPC with multipleangle laser scattering detection.

[0062] The silicone chains preferred for use to substitute or replace(dependent upon the synthetic route use to prepare the substitutedpolysaccharides of the invention) at least one —OR group in thecompounds of formula (I) are representative of preferred silicone chainsfor use in substituted polysaccharides used in the invention as a whole,ie whether or not the overall structure conforms to Formula (I).

[0063] Preferably, the average degree of substitution for the siliconechains is from 0.001 to 0.5, preferably 0.01 to 0.5, more preferablyfrom 0.01 to 0.1, still more preferably from 0.01 to 0.05.

[0064] Even more preferably the average degree of substitution for thesilicone chains is from 0.00001 to 0.1, more preferably from 0.001 to0.04, even more preferably from 0.001 to 0.01.

[0065] Preferred silicone chains suitable for this use are those offormula:

[0066] wherein L is absent or is a linking group and one or two ofsubstituents G¹-G³ is a methyl group, the remainder being selected fromgroups of formula

[0067] the —Si(CH₃)₂O— groups and the —Si(CH₃O)(G⁴)— groups beingarranged in random or block fashion, but preferably random.

[0068] wherein n is from 5 to 1000, preferably from 10 to 200 and m isfrom 0 to 100, preferably from 0 to 20, for example from 1 to 20.

[0069] G⁴ is selected from groups of formula:

[0070] —(CH₂)_(P)—CH₃, where p is from 1 to 18

[0071] —(CH₂)_(q)—NH—(CH₂)_(r), —NH₂ where q and r are independentlyfrom 1 to 3

[0072] —(CH₂)_(s)—NH₂, where s is from 1 to 3

[0073]  where t is from 1 to 3

[0074] —(CH₂)_(u)—COOH, where u is from 1 to 10,

[0075]  where v is from 1 to 10, and

[0076] —(CH₂CH₂O)_(w)—(CH₂)_(x)H, where w is from 1 to 150, preferablyfrom 10 to 20 and x is from 0 to 10;

[0077] and G⁵ is independently selected from hydrogen, groups definedabove for G⁴,—OH,—CH₃ and —C(CH₃)₃.

[0078] Other substituents

[0079] As well as the silicone chain(s) and the pendant group(s) whichundergo a chemical change to enhance deposition, pendant groups of othertypes may optionally be present, i.e. groups which do not confer abenefit and which do not undergo a chemical change to enhance substrateaffinity. Within that class of other groups is the sub-class of groupsfor enhancing the solubility of the material (e.g. groups which are, orcontain one or more free carboxylic acid/salt and/or sulphonic acid/saltand/or sulphate groups).

[0080] Examples of solubility enhancing substituents include carboxyl,sulphonyl, hydroxyl, (poly)ethyleneoxy- and/or(poly)propyleneoxy-containing groups, as well as amine groups.

[0081] The other pendant groups preferably comprise from 0% to 65%, morepreferably from 0% to 10% of the total number of pendant groups. Thewater-solubilising groups could comprise from 0% to 100% of those othergroups but preferably from 0% to 20%, more preferably from 0% to 10%,still more preferably from 0% to 5% of the total number of other pendantgroups.

[0082] Synthetic Routes

[0083] As described above, preferred substituted polysaccharides of thepresent invention are those of formula (I). Further, preferred siliconechains, whether for the compounds of formula (I) or any othersubstituted polysaccharides of the invention are preferably attached viaa linking group “-L-”. This linking group is the residue of thereactants-used to form the substituted polysaccharide.

[0084] The substituted polysaccharides of the invention can be madethus:

[0085] (a) a polysaccharide is first substituted with one or moredeposition enhancing groups; and

[0086] (b) one or more silicone groups are then attached.

[0087] If any other substituents are to be present, these may already bepresent in the commercially available polysaccharide, or attached beforeor after step (a) and/or (b).

[0088] Whilst steps (a) and (b) can be reversed, the reaction wherebystep (a) is conducted first is preferred.

[0089] The deposition enhancing group(s) is/or are attached in step (a)according to the methodology described in WO-A-00/18861.

[0090] In step (b), one or more hydroxyl groups on the polysaccharideare reacted with a reactive group attached to the silicone chain, or thehydroxyl group(s) in question is/are converted to another group capableof reaction with a reactive group attached to the silicone chain. Listedbelow, are suitable mutually reactive groups. In the case of hydroxylgroups, these may be the original hydroxyl group of the polysaccharide.However, either of a pair of these mutually reactive groups may bepresent on the polysaccharide and the other attached to the siliconechain, or vice versa, the reaction chemistry being chosen appropriately.In the following description, for convenience, “PSC” refers to thepolysaccharide chain with or without deposition enhancing group(s)and/or other substituent(s) already attached. “SXC” refers to the group

[0091] as hereinbefore defined.

[0092] Preferred linking groups —L— are selected from the following,wherein preferably, the left hand end of the group depicted is connectedto the saccharide ring either direct or via the residual oxygen of oneof the original saccharide —OH groups and the right hand end isconnected to the moiety —Si(G¹G²G³). Thus, the configuration as writtenis PSC-L-SXC. However, the reverse configuration SXC-L-PSC is alsowithin the ambit of this definition and this is also mentioned whereappropriate.

[0093] Preferred linking groups -L- are selected from amide, ester,ether, urethane, triazine, carbonate, amine and ester-alkylene linkages.

[0094] A preferred amide linkage is:

[0095] where G⁶ and G⁷ are each optionally present and are independentlyselected spacer groups, e.g. selected from C₁₋₁₄ alkylene groups,arylene, C₁₋₄ alkoxylene, a residue of an oligo- or poly-ethylene oxidemoiety, C₁₋₄ alkylamine or a polyamine groups and

[0096] G⁸ is hydrogen or C₁₋₄ alkyl.

[0097] This linkage can be formed by reacting

[0098] wherein G⁷ and G⁸ are as hereinbefore defined and G⁹ is hydrogenor C₁₋₄ alkyl;

[0099] with a compound of formula:

[0100] wherein G¹¹ is hydroxy, a group with active ester functionalityhalo, or a leaving group suitable for neucleophilie displacement such asimidazole or an imidazole-containing group and wherein G⁶ ishereinbefore defined above, or —CO-G¹¹is replaced by a cyclic acidanhydride. Active ester synthesis is described in M. Bodanszky, “ThePeptides”, Vol.1, Academic Press Inc., 1975, pp105 ff.

[0101] The reverse configuration linkage may be formed by reacting

[0102] wherein G¹² is a ring-opened carboxylic acid anhydride,phenylene, or a group of formula

[0103] and G¹¹ is as hereinbefore defined;

[0104] with the group of formula

[0105] where G⁶ and G⁸ are as hereinbefore defined.

[0106] A preferred ester linkage has the formula

[0107] wherein G⁶ and G⁷ are as hereinbefore defined, G⁶ optionallybeing absent.

[0108] This may be formed by reacting

[0109] wherein G¹¹ and G¹² are as hereinbefore defined with

[0110] wherein G⁶ is as hereinbefore defined.

[0111] The reverse ester linkage formation may be formed by reacting

[0112] (i.e. the optionally modified polysacharide with at least oneresidual —OH group) with

[0113] wherein G⁶ and G¹¹ are as hereinbefore defined, or —CO-G¹¹ may bereplaced by a cyclic anhydride.

[0114] Preferred ether linkages have the formula

—G⁶—O—G⁷—

[0115] wherein G⁶ and G⁷ are as hereinbefore defined, optionally onebeing absent.

[0116] This linkage may be formed by reacting

PSC-G-OH

[0117] with

[0118] wherein G¹⁵ is C₁₋₄ alkylene and G⁶ is optionally absent and isas hereinbefore defined.

[0119] A preferred urethane linkage is

[0120] wherein G⁶ and G⁷ are as hereinbefore defined, G⁶ optionallybeing absent (preferably absent in the configuration PSC-L-SXC)

PSC-G⁶-OH

SXC-G⁷-NCO

[0121] with

[0122] wherein G⁶ and G⁷ are as hereinbefore defined, G⁶ optionallybeing absent (preferably absent in the configuration PSC-L-SXC)

[0123] The reverse configuration is also possible but the simplestarrangement is PSC-L-SXC and wherein G⁶ is absent. Also most common iswhen G⁷ is alkylene.

[0124] The latter compound is made by reacting

SXC G⁷NH₂

[0125] wherein G⁷ is as hereinbefore defined;

[0126] with phosgene.

[0127] Another route is to react

PSC-G⁶-OH

[0128] wherein G⁶ is as hereinbefore defined

[0129] with carbonyl dimidazole to form

[0130] and react that product with

SXC-G⁷-NH₂

[0131] wherein G⁷ is as hereinbefore defined.

[0132] Preferred triazine linkages have the formula

[0133] wherein G⁶ and G⁷ are as hereinbefore defined, G⁶ optionallybeing absent.

[0134] These linkages may be formed by reacting

SXC-G⁷-OH

or

SXC-G⁷-NH₂

[0135] wherein G⁷ is as hereinbefore defined with cyanuic chloride andthen with

PSC-G-OH

[0136] wherein G⁸ is as hereinbefore defined but may be absent;

[0137] or (reverse -L-) by reacting

PSC G⁷-OH

[0138] with cyanuric chloride (when G⁷ is as hereinbefore defined) andthen with

SXC-G⁶-OH

or

SXC-G⁶-NH₂

[0139] Preferred carbonate linkages have the formula

[0140] wherein G⁶ is as hereinbefore defined.

[0141] This linkage may be formed by reacting

PSC-OH

[0142] with

SXC-G⁶-OH

[0143] in the presence of carbonyl dimidazole or phosgene

[0144] Preferred amine linkages have the formula

[0145] wherein G⁶, G⁷, G⁸, G⁹ and G¹⁵ are as hereinbefore defined.

[0146] This linkage may be formed by reacting

[0147] wherein G⁶-G⁹ are hereinbefore defined;

[0148] with

[0149] wherein G¹⁵ is as hereinbefore defined.

[0150] Preferred ester-alkylene linkages have the formula

[0151] wherein G⁷ is as hereinbefore defined.

[0152] These linkages may be prepared by reacting

PSC-OH

[0153] with

[0154] and then reacting with a hydrogen-terminated silicone chaincompound (i.e. G=H) over a platinum catalyst.

[0155] Compositions

[0156] The substituted polysaccharide according to the first aspect ofthe present invention may be incorporated into compositions containingonly a diluent (which may comprise solid and/or liquid) and/or alsocomprising an active ingredient. The compound is typically included insaid compositions at levels of from 0.01% to 25% by weight, preferablyfrom 0.1% to 10%, most preferably from 0.5% to 3%.

[0157] The active ingredient in the compositions is preferably a surfaceactive agent or a fabric conditioning agent. More than one activeingredient may be included. For some applications a mixture of activeingredients may be used.

[0158] The compositions of the invention may be in any physical forme.g. a solid such as a powder or granules, a tablet, a solid bar, apaste, gel or liquid, especially, an aqueous based liquid. In particularthe compositions may be used in laundry compositions, especially inliquid, powder or tablet laundry composition. The compositions of thepresent invention are preferably laundry compositions, especially mainwash (fabric washing) compositions or rinse-added softeningcompositions. The main wash compositions may include a fabric softeningagent and rinse-added fabric softening compositions may includesurface-active compounds, particularly non-ionic surface-activecompounds, if appropriate.

[0159] The detergent compositions of the invention may contain asurface-active compound (surfactant) which may be chosen from soap andnon-soap anionic, cationic, non-ionic, amphoteric and zwitterionicsurface-active compounds and mixtures thereof. Many suitablesurface-active compounds are available and are fully described in theliterature, for example, in “Surface-Active Agents and Detergents”,Volumes 1 and 11, by Schwartz, Perry and Berch.

[0160] The preferred detergent-active compounds that can be used aresoaps and synthetic non-soap anionic and non-ionic compounds.

[0161] The compositions of the invention may contain linear alkylbenzenesulphonate, particularly linear alkylbenzene sulphonates having an alkylchain length of C₈-C₁₅. It is preferred if the level of linearalkylbenzene sulphonate is from 0 wt % to 30 wt %, more preferably 1 wt% to 25 wt %, most preferably from 2 wt % to 15 wt %.

[0162] The compositions of the invention may contain other anionicsurfactants in amounts additional to the percentages quoted above.Suitable anionic surfactants are well-known to those skilled in the art.Examples include primary and secondary alkyl sulphates, particularlyC₈-C₁₅ primary alkyl sulphates; alkyl ether sulphates; olefinsulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; andfatty acid ester sulphonates. Sodium salts are generally preferred.

[0163] The compositions of the invention may also contain non-ionicsurfactant. Nonionic surfactants that may be used include the primaryand secondary alcohol ethoxylates, especially the C₈-C₂₀ aliphaticalcohols ethoxylated with an average of from 1 to 20 moles of ethyleneoxide per mole of alcohol, and more especially the C₁₀-C₁₅ primary andsecondary aliphatic alcohols ethoxylated with an average of from 1 to 10moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionicsurfactants include alkylpolyglycosides, glycerol monoethers, andpolyhydroxyamides (glucamide).

[0164] It is preferred if the level of non-ionic surfactant is from 0 wt% to 30 wt %, preferably from 1 wt % to 25 wt %, most preferably from 2wt % to 15 wt %.

[0165] Any conventional fabric conditioning agent may be used in thecompositions of the present invention. The conditioning agents may becationic or non-ionic. If the fabric conditioning compound is to beemployed in a main wash detergent composition the compound willtypically be non-ionic. For use in the rinse phase, typically they willbe cationic. They may for example be used in amounts from 0.5% to 35%,preferably from 1% to 30% more preferably from 3% to 25% by weight ofthe composition.

[0166] Suitable cationic fabric softening compounds are substantiallywater-insoluble quaternary ammonium materials comprising a single alkylor alkenyl long chain having an average chain length greater than orequal to C₂₀ or, more preferably, compounds comprising a polar headgroup and two alkyl or alkenyl chains having an average chain lengthgreater than or equal to C₁₄. Preferably the fabric softening compoundshave two long chain alkyl or alkenyl chains each having an average chainlength greater than or equal to C₁₆. Most preferably at least 50% of thelong chain alkyl or alkenyl groups have a chain length of C₁₈ or above.It is preferred if the long chain alkyl or alkenyl groups of the fabricsoftening compound are predominantly linear.

[0167] Quaternary ammonium compounds having two long-chain aliphaticgroups, for example, distearyidimethyl ammonium chloride and di(hardenedtallow alkyl) dimethyl ammonium chloride, are widely used incommercially available rinse conditioner compositions. Other examples ofthese cationic compounds are to be found in “Surfactants Science Series”volume 34 ed. Richmond 1990, volume 37 ed. Rubingh 1991 and volume 53eds. Cross and Singer 1994, Marcel Dekker Inc. New York”.

[0168] Any of the conventional types of such compounds may be used inthe compositions of the present invention. The fabric softeningcompounds are preferably compounds that provide excellent softening, andare characterised by a chain melting L_(β) to L_(α) transitiontemperature greater than 25° C., preferably greater than 35° C., mostpreferably greater than 45° C. This L_(β) to L_(α), transition can bemeasured by differential scanning calorimetry as defined in “Handbook ofLipid Bilayers”, D Marsh, CRC Press, Boca Raton, Fla., 1990 (pages 137and 337).

[0169] Substantially water-insoluble fabric softening compounds aredefined as fabric softening compounds having a solubility of less than1×10⁻³ wt % in demineralised water at 20° C. Preferably the fabricsoftening compounds have a solubility of less than 1×₁₀-4 wt %, morepreferably less than 1×10⁻⁸ to 1×10⁻⁶ wt %.

[0170] Especially preferred are cationic fabric softening compounds thatare water-insoluble quaternary ammonium materials having two C₁₂₋₂₂alkyl or alkenyl groups connected to the molecule via at least one esterlink, preferably two ester links. An especially preferred ester-linkedquaternary ammonium material can be represented by the formula:

[0171] wherein each R₅ group is independently selected from C₁₋₄ alkylor hydroxyalkyl groups or C₂₋₄ alkenyl groups; each R₆ group isindependently selected from C₈₋₂₈ alkyl or alkenyl groups; and whereinR₇ is a linear or branched alkylene group of 1 to 5 carbon atoms, T is

[0172] and p is 0 or is an integer from 1 to 5.

[0173] Di(tallowoxyloxyethyl) dimethyl ammonium chloride and/or itshardened tallow analogue is an especially preferred compound of thisformula.

[0174] A second preferred type of quaternary ammonium material can berepresented by the formula:

[0175] wherein R₅, p and R₆ are as defined above.

[0176] A third preferred type of quaternary ammonium material are thosederived from triethanolamine (hereinafter referred to as ‘TEA quats’) asdescribed in for example U.S. Pat. No. 3,915,867 and represented byformula:

(TOCH₂CH₂)₃N+(R₉)

[0177] wherein T is H or (R₈—CO—) where R₈ group is independentlyselected from C₈₋₂₈ alkyl or alkenyl groups and R₉ is C₁₋₄ alkyl orhydroxyalkyl groups or C₂₋₄ alkenyl groups. For example N-methyl-N,N,N-triethanolamine ditallowester or di-hardened-tallowester quaternaryammonium chloride or methosulphate. Examples of commercially availableTEA quats include Rewoquat WE18 and Rewoquat WE20, both partiallyunsaturated (ex. WITCO), Tetranyl AOT-1, fully saturated (ex. KAO) andStepantex VP 85, fully saturated (ex. Stepan).

[0178] It is advantageous if the quaternary ammonium material isbiologically biodegradable. Preferred materials of this class such as1,2-bis(hardened tallowoyloxy)-3-trimethylammonium propane chloride andtheir methods of preparation are, for example, described in U.S. Pat.No. 4,137,180 (Lever Brothers Co). Preferably these materials comprisesmall amounts of the corresponding monoester as described in U.S. Pat.No. 4,137,180, for example, 1-hardenedtallowoyloxy-2-hydroxy-3-trimethylammonium propane chloride.

[0179] Other useful cationic softening agents are alkyl pyridinium saltsand substituted imidazoline species. Also useful are primary, secondaryand tertiary amines and the condensation products of fatty acids withalkylpolyamines.

[0180] The compositions may alternatively or additionally containwater-soluble cationic fabric softeners, as described in GB 2 039 556B(Unilever).

[0181] The compositions may comprise a cationic fabric softeningcompound and an oil, for example as disclosed in EP-A-0829531.

[0182] The compositions may alternatively or additionally containnonionic fabric softening agents such as lanolin and derivativesthereof.

[0183] Lecithins and other phospholipids are also suitable softeningcompounds.

[0184] In fabric softening compositions nonionic stabilising agent maybe present. Suitable nonionic stabilising agents may be present such aslinear C₈ to C₂₋₂ alcohols alkoxylated with 10 to 20 moles of alkyleneoxide, C₁₀ to C₂₋₀ alcohols, or mixtures thereof. Other stabilisingagents include the deflocculating polymers as described in EP 0415698A2and EP 0458599 B1.

[0185] Advantageously the nonionic stabilising agent is a linear C₈ toC₂₋₂ alcohol alkoxylated with 10 to 20 moles of alkylene oxide.Preferably, the level of nonionic stabiliser is within the range from0.1 to 10% by weight, more preferably from 0.5 to 5% by weight, mostpreferably from 1 to 4% by weight. The mole ratio of the quaternaryammonium compound and/or other cationic softening agent to the nonionicstabilising agent is suitably within the range from 40:1 to about 1 :1,preferably within the range from 18:1 to about 3:1.

[0186] The composition can also contain fatty acids, for example C₈ toC₂₋₄ alkyl or alkenyl monocarboxylic acids or polymers thereof.Preferably saturated fatty acids are used, in particular, hardenedtallow C₁₆ to C₁₈ fatty acids. Preferably the fatty acid isnon-saponified, more preferably the fatty acid is free, for exampleoleic acid, lauric acid or tallow fatty acid. The level of fatty acidmaterial is preferably more than 0.1% by weight, more preferably morethan 0.2% by weight. Concentrated compositions may comprise from 0.5 to20% by weight of fatty acid, more preferably 1% to 10% by weight. Theweight ratio of quaternary ammonium material or other cationic softeningagent to fatty acid material is preferably from 10:1 to 1:10.

[0187] It is also possible to include certain mono-alkyl cationicsurfactants which can be used in main-wash compositions for fabrics.Cationic surfactants that may be used include quaternary ammonium saltsof the general formula R₁R₂R₃R₄N⁺X⁻ wherein the R groups are long orshort hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylatedalkyl groups, and X is a counter-ion (for example, compounds in which R₁is a C₈-C₂₂ alkyl group, preferably a C₈-C₁₀ or C₁₂-C₁₄ alkyl group, R₂is a methyl group, and R₃ and R₄, which may be the same or different,are methyl or hydroxyethyl groups); and cationic esters (for example,choline esters).

[0188] The choice of surface-active compound (surfactant), and theamount present, will depend on the intended use of the detergentcomposition. In fabric washing compositions, different surfactantsystems may be chosen, as is well known to the skilled formulator, forhandwashing products and for products intended for use in differenttypes of washing machine.

[0189] The total amount of surfactant present will also depend on theintended end use and may be as high as 60 wt %, for example, in acomposition for washing fabrics by hand. In compositions for machinewashing of fabrics, an amount of from 5 to 40 wt % is generallyappropriate. Typically the compositions will comprise at least 2 wt %surfactant e.g. 2-60%, preferably 15-40% most preferably 25-35%.

[0190] Detergent compositions suitable for use in most automatic fabricwashing machines generally contain anionic non-soap surfactant, ornon-ionic surfactant, or combinations of the two in any suitable ratio,optionally together with soap.

[0191] The compositions of the invention, when used as main wash fabricwashing compositions, will generally also contain one or more detergencybuilders. The total amount of detergency builder in the compositionswill typically range from 5 to 80 wt %, preferably from 10 to 60 wt %.

[0192] Inorganic builders that may be present include sodium carbonate,if desired in combination with a crystallisation seed for calciumcarbonate, as disclosed in GB 1 437 950 (Unilever); crystalline andamorphous aluminosilicates, for example, zeolites as disclosed in GB 1473 201 (Henkel), amorphous aluminosilicates as disclosed in GB 1 473202 (Henkel) and mixed crystalline/amorphous aluminosilicates asdisclosed in GB 1 470 250 (Procter & Gamble); and layered silicates asdisclosed in EP 164 514B (Hoechst). Inorganic phosphate builders, forexample, sodium orthophosphate, pyrophosphate and tripolyphosphate arealso suitable for use with this invention.

[0193] The compositions of the invention preferably contain an alkalimetal, preferably sodium, aluminosilicate builder. Sodiumaluminosilicates may generally be incorporated in amounts of from 10 to70% by weight (anhydrous basis), preferably from 25 to 50 wt %.

[0194] The alkali metal aluminosilicate may be either crystalline oramorphous or mixtures thereof, having the general formula: 0.8-1.5Na₂O.Al₂O₃.0.8-6 SiO₂

[0195] These materials contain some bound water and are required to havea calcium ion exchange capacity of at least 50 mg CaO/g. The preferredsodium aluminosilicates contain 1.5-3.5 SiO₂ units (in the formulaabove). Both the amorphous and the crystalline materials can be preparedreadily by reaction between sodium silicate and sodium aluminate, asamply described in the literature. Suitable crystalline sodiumaluminosilicate ion-exchange detergency builders are described, forexample, in GB 1 429 143 (Procter & Gamble). The preferred sodiumaluminosilicates of this type are the well-known commercially availablezeolites A and X, and mixtures thereof.

[0196] The zeolite may be the commercially available zeolite 4A nowwidely used in laundry detergent powders. However, according to apreferred embodiment of the invention, the zeolite builder incorporatedin the compositions of the invention is maximum aluminium zeolite P(zeolite MAP) as described and claimed in EP 384 070A (Unilever).Zeolite MAP is defined as an alkali metal aluminosilicate of the zeoliteP type having a silicon to aluminium ratio not exceeding 1.33,preferably within the range of from 0.90 to 1.33, and more preferablywithin the range of from 0.90 to 1.20.

[0197] Especially preferred is zeolite MAP having a silicon to aluminiumratio not exceeding 1.07, more preferably about 1.00. The calciumbinding capacity of zeolite MAP is generally at least 150 mg CaO per gof anhydrous material.

[0198] Organic builders that may be present include polycarboxylatepolymers such as polyacrylates, acrylic/maleic copolymers, and acrylicphosphinates; monomeric polycarboxylates such as citrates, gluconates,oxydisuccinates, glycerol mono-, di and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates,hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates;and sulphonated fatty acid salts. This list is not intended to beexhaustive.

[0199] Especially preferred organic builders are citrates, suitably usedin amounts of from 5 to 30 wt %, preferably from 10 to 25 wt %; andacrylic polymers, more especially acrylic/maleic copolymers, suitablyused in amounts of from 0.5 to 15 wt %, preferably from 1 to 10 wt %.

[0200] Builders, both inorganic and organic, are preferably present inalkali metal salt, especially sodium salt, form.

[0201] Compositions according to the invention may also suitably containa bleach system. Fabric washing compositions may desirably containperoxy bleach compounds, for example, inorganic persalts or organicperoxyacids, capable of yielding hydrogen peroxide in aqueous solution.

[0202] Suitable peroxy bleach compounds include organic peroxides suchas urea peroxide, and inorganic persalts such as the alkali metalperborates, percarbonates, perphosphates, persilicates and persulphates.Preferred inorganic persalts are sodium perborate monohydrate andtetrahydrate, and sodium percarbonate.

[0203] Especially preferred is sodium percarbonate having a protectivecoating against destabilisation by moisture. Sodium percarbonate havinga protective coating comprising sodium metaborate and sodium silicate isdisclosed in GB 2 123 044B (Kao).

[0204] The peroxy bleach compound is suitably present in an amount offrom 0.1 to 35 wt %, preferably from 0.5 to 25 wt %. The peroxy bleachcompound may be used in conjunction with a bleach activator (bleachprecursor) to improve bleaching action at low wash temperatures. Thebleach precursor is suitably present in an amount of from 0.1 to 8 wt %,preferably from 0.5 to 5 wt %.

[0205] Preferred bleach precursors are peroxycarboxylic acid precursors,more especially peracetic acid precursors and pernoanoic acidprecursors. Especially preferred bleach precursors suitable for use inthe present invention are N,N,N′,N′,-tetracetyl ethylenediamine (TAED)and sodium nonanoyloxybenzene sulphonate (SNOBS). The novel quaternaryammonium and phosphonium bleach precursors disclosed in U.S. Pat. No.4,751,015 and U.S. Pat. No. 4,818,426 (Lever Brothers Company) and EP402 971A (Unilever), and the cationic bleach precursors disclosed in EP284 292A and EP 303 520A (Kao) are also of interest.

[0206] The bleach system can be either supplemented with or replaced bya peroxyacid. examples of such peracids can be found in U.S. Pat. No.4,686,063 and U.S. Pat. No. 5,397,501 (Unilever). A preferred example isthe imido peroxycarboxylic class of peracids described in EP A 325 288,EP A 349 940, DE 382 3172 and EP 325 289. A particularly preferredexample is phthalimido peroxy caproic acid (PAP). Such peracids aresuitably present at 0.1-12%, preferably 0.5-10%.

[0207] A bleach stabiliser (transition metal sequestrant) may also bepresent. Suitable bleach stabilisers include ethylenediaminetetra-acetate (EDTA), the polyphosphonates such as Dequest (Trade Mark)and non-phosphate stabilisers such as EDDS (ethylene diamine di-succinicacid). These bleach stabilisers are also useful for stain removalespecially in products containing low levels of bleaching species or nobleaching species.

[0208] An especially preferred bleach system comprises a peroxy bleachcompound (preferably sodium percarbonate optionally together with ableach activator), and a transition metal bleach catalyst as describedand claimed in EP 458 397A, EP 458 398A and EP 509 787A (Unilever).

[0209] The compositions according to the invention may also contain oneor more enzyme(s). Suitable enzymes include the proteases, amylases,cellulases, oxidases, peroxidases and lipases usable for incorporationin detergent compositions. Preferred proteolytic enzymes (proteases)are, catalytically active protein materials which degrade or alterprotein types of stains when present as in fabric stains in a hydrolysisreaction. They may be of any suitable origin, such as vegetable, animal,bacterial or yeast origin. Proteolytic enzymes or proteases of variousqualities and origins and having activity in various pH ranges of from4-12 are available and can be used in the instant invention. Examples ofsuitable proteolytic enzymes are the subtilisins which are obtained fromparticular strains of B. Subtilis B. licheniformis, such as thecommercially available subtilisins Maxatase (Trade Mark), as supplied byGenencor International N.V., Delft, Holland, and Alcalase (Trade Mark),as supplied by Novozymes Industri A/S, Copenhagen, Denmark.

[0210] Particularly suitable is a protease obtained from a strain ofBacillus having maximum activity throughout the pH range of 8-12, beingcommercially available, e.g. from Novozymes Industri A/S under theregistered trade-names Esperase (Trade Mark) and Savinase (Trade-Mark).The preparation of these and analogous enzymes is described in GB 1 243785. Other commercial proteases are Kazusase (Trade Mark obtainable fromShowa-Denko of Japan), Optimase (Trade Mark from Miles Kali-Chemie,Hannover, West Germany), and Superase (Trade Mark obtainable from Pfizerof U.S.A.).

[0211] Detergency enzymes are commonly employed in granular form inamounts of from about 0.1 to about 3.0 wt %. However, any suitablephysical form of enzyme may be used.

[0212] The compositions of the invention may contain alkali metal,preferably sodium carbonate, in order to increase detergency and easeprocessing. Sodium carbonate may suitably be present in amounts rangingfrom 1 to 60 wt %, preferably from 2 to 40 wt %. However, compositionscontaining little or no sodium carbonate are also within the scope ofthe invention.

[0213] Powder flow may be improved by the incorporation of a smallamount of a powder structurant, for example, a fatty acid (or fatty acidsoap), a sugar, an acrylate or acrylate/maleate copolymer, or sodiumsilicate. One preferred powder structurant is fatty acid soap, suitablypresent in an amount of from 1 to 5 wt %.

[0214] Other materials that may be present in detergent compositions ofthe invention include sodium silicate; antiredeposition agents such ascellulosic polymers; soil release polymers; inorganic salts such assodium sulphate; or lather boosters as appropriate; proteolytic andlipolytic enzymes; dyes; coloured speckles; fluorescers and decouplingpolymers. This list is not intended to be exhaustive. However, many ofthese ingredients will be better delivered as benefit agent groups inmaterials according to the first aspect of the invention.

[0215] The detergent composition when diluted in the wash liquor (duringa typical wash cycle) will typically give a pH of the wash liquor from 7to 10.5 for a main wash detergent.

[0216] Particulate detergent compositions are suitably prepared byspray-drying a slurry of compatible heat-insensitive ingredients, andthen spraying on or post-dosing those ingredients unsuitable forprocessing via the slurry. The skilled detergent formulator will have nodifficulty in deciding which ingredients should be included in theslurry and which should not.

[0217] Particulate detergent compositions of the invention preferablyhave a bulk density of at least 400 g/l, more preferably at least 500g/l. Especially preferred compositions have bulk densities of at least650 g/litre, more preferably at least 700 g/litre.

[0218] Such powders may be prepared either by post-tower densificationof spray-dried powder, or by wholly non-tower methods such as dry mixingand granulation; in both cases a high-speed mixer/granulator mayadvantageously be used. Processes using high-speed mixer/granulators aredisclosed, for example, in EP 340 013A, EP 367 339A, EP 390 251A and EP420 317A (Unilever).

[0219] Liquid detergent compositions can be prepared by admixing theessential and optional ingredients thereof in any desired order toprovide compositions containing components in the requisiteconcentrations. Liquid compositions according to the present inventioncan also be in compact form which means it will contain a lower level ofwater compared to a conventional liquid detergent.

[0220] Substrate

[0221] The substrate may be any substrate onto which it is desirable todeposit silicones and which is subjected to treatment such as a washingor rinsing process.

[0222] In particular, the substrate may be a textile fabric, fabric,preferably of cotton.

[0223] It has been found that particular good results are achieved whenusing a natural fabric substrate such as cotton, or fabric blendscontaining cotton.

[0224] Treatment

[0225] The treatment of the substrate with the material of the inventioncan be made by any suitable method such as washing, soaking or rinsingof the substrate.

[0226] Typically the treatment will involve a washing or rinsing methodsuch as treatment in the main wash or rinse cycle of a washing machineand involves contacting the substrate with an aqueous medium comprisingthe material of the invention.

[0227] The present invention will now be explained in more detail byreference to the following non-limiting examples:—

[0228] In the following examples where percentages are metioned, this isto be understood as percentage by weight. In the following tables wherethe values do not add up to 100 these are to be understood as parts byweight.

EXAMPLE 1 Sample Synthesis of an Ester Linked Cellulose Monoacetate(CMA) Silicone

[0229] Monocarboxydecyl terminated polydimethylsiloxane (PDMS) source(Mwt 5,000: 1.5 g, 0.23 mmols) was dispersed in dimethylacetamide (10cm³) by vigorous stirring under nitrogen. Carbonyldiimidazole (37 mg,0.23 mmols) was then added and the dispersion heated with stirring to70° C. under nitrogen for two hours. A solution of cellulose monoacetate(DS 0.58; 1 g, 5.3 mmol equivalents based on primary hydroxyl groups) indimethylacetamide (10 cm³) was then added and stirring and heating wascontinued for a further 20 hours. Following this time the mixture wasfiltered and the filtrate added to vigorously stirring acetone to give awhite precipitate. This precipitate was filtered off, washed withacetone and dried under vacuum to give a white polymer (1.01 g). Fromthe ¹H NMR of the polymer (after hydrolysis of 20% DCl in D₂O for twohours at 80° C.) and normalising the integration of the anomeric protonsto unity and the acetate group to 0.58 the S₁—CH₃ group (at 0.0 ppm)integration gives an overall degree of substitution (DS) of siloxanegroup as 0.04.

EXAMPLE 2 Preparation of PDMS-Grafted Cellulose Monoacetate Attachmentof PDMS via a Carbonate Linkage

[0230] Carbinol (hydroxyl) terminated PDMS (Mwt 5,000; 11.5 g, 2.3 mmol)was dispersed in anhydrous dimethylacetamide (20 cm³) with % of a sodiumhydroxide pellet. The solution was stirred with heating (60° C.) undernitrogen for 30 mins prior to the addition of 1,1′-carbonyldiimidazole(0.74 g, 4.6 mmols). After two hours a solution of cellulose monoacetate(10 g) in dimethylacetamide (100 cm³) was added and stirring the heatingwas continued for a further 18 hours. The solution was then allowed tocool at room temperature and added slowly to vigorously stirring acetone(500 cm³) to give a light brown precipitate, the polymer was filteredoff and washed with acetate by continuous extraction for 18 hours.Finally, the polymer was dried under vacuum at 40° C. for 18 hours togive a light tan solid (3.87 g). From the ¹H NMR of the polymer (afterhydrolysis in 20% DCl in D₂O for an hour at 80° C.) and normalising theintegration of the anomeric protons to unity and the acetate group to0.58 the S₁—CH₃ group (at 0.0 ppm) integration gives an overall DS ofthe PDMS group as 0.0063.

EXAMPLE 3 Preparation of PDMS-Grafted Cellulose Monoacetate Attachmentof PDMS via a Carbamate Linkage

[0231] Cellulose monoacetate (10 g) was dissolved in anhydrousdimethylacetamide (100 Cm³) with stirring and heating (60° C.) undernitrogen, 1,1′-carbonyldiimidazole (0.74 g, 4.6 mmols) and {fraction(1/4)} of a sodium hydroxide was then added and the solution was stirredand heated for a further 2 hours. A solution of aminopropyl terminatedPDMS (Mwt 1,000; 6.9 g. 6.0 mmols) in dimethylacetamide (50 cm³) wasthen added and the solution was stirred with heating for a further 18hours. The resulting slurry was then centrifuged and the supernatantadded dropwise the vigorously stirring acetone (500 cm³) to give anoff-white polymer. The precipitate was filtered off, washed with acetone(300 cm³) and dried under vacuum (40° C.) to give a tan-coloured solid(2.2 g). From the ¹H NMR of the polymer (after hydrolysis in 20% DCl inD₂O for an hour at 80° C.) and normalising the integration of theanomeric protons to unity and the acetate group to 0.58 the S₁—CH₃ group(at 0.0 ppm) integration gives an overall DS of the PDMS group as 0.039.

EXAMPLE 4 Use of CMA-Silicone in a Detergent Formulation to Give aFabric Cares Benefit.

[0232] Formulations Quantity/Parts by Weight Ingredient Example ControlA NaLAS 20.9 20.9 C₁₂₋₁₅ 7EO alcohol 20.9 20.9 ethoxylate SodiumCarbonate 31.3 31.3 Sodium Bicarbonate 10.2 10.2 Polymer A 16.7 —Polymer B — 16.7

[0233] Wash liquors were prepared at 40° C. in each of two Rotawash potsconsisting of 200 cm³ of water (16° French Hard) to which had beenadded, 0.478 g of either the Example formulation or the controlformulation A. To each pot was also added one piece (20 cm×20 cm) ofwhite mercerised woven cotton and one piece (20 cm×20 cm) of a similarcotton dyed at a 1% level with Direct Red 80. The fabrics were washedfor 30 minutes at 40° C. using a standard agitation rate of 40 rpm. Atthe end of the wash, each set of fabrics was rinsed with 2 changes of1000 cm³ of water (20° C., 16° French Hard). The fabric sets wereair-dried at ambient temperature and then each set was subjected to thesame wash procedure up to five times. After drying for the fifth washthe “white” cloths from each wash condition were then stored in ahumidity-controlled room (65° C. Humidity 23° C. Temperature) for 24 hrsto equilibrate. After this time the cloths were measured on the KawabataShear machine, to obtain shear hysterisis parameters as the 2HG5 values.This value is a measure of the lubricity between fibres and yarns of thefabric and has been correlated to both softness and creasereduction(REF: The use of Kawabata Instrumentation to evaluate Siliconefabric softeners by A. J. Sabia and A. M. Pagliuchi). The lower the 2HG5value the greater the softness of the fabric. Kawabata 2HG5 resultsExample Formulation Control Formulation White cloth from wash 5 6.156.83

[0234] Formulation Examples:

[0235] Examples 5-8 are formulation examples. In each case “Polymer A”refers, respectively, to the materials specified in Examples 1 or 2.

[0236] Raw material specification: Component Specification LAS AlkylBenzene Sulphonic-acid, Marlon AS3, ex Huls Na-PAS Primary Alkyl BenzeneSulphonic-acid, neutralised with NaOH Dobanol 25-7 C₁₂₋₁₅ ethoxylatedalcohol, 7EO, ex shell Zeolite Wassalith P, ex Degussa STPP Sodium TriPolyphosphate, Thermphos NW, ex Hoechst Dequest 2066 Metal chelatingagent, ex Monsanto Lipolase Type 100L, ex Novo Savinase 16L Protease, exNovo Sokalan CP5 Acrylic/Maleic Builder Polymer, ex BASF DefloculatingPolymer A-11 disclosed in EP-A-346 995 Polymer SCMC Sodium CarboxymethylCellulose Minors Antiredeposition polymers, transition- matalscavangers/bleach stabilisers, fluorescers, dye-transfer-inhibitionpolymers, enzymes, Polymer A Material Specified in Example 1.

EXAMPLE 5 Spray-Dried Powder

[0237] Component % w/w Na PAS 11.5 Dobanol 25-7 6.3 Soap 2 Zeolite 24.1SCMC 0.6 Na Citrate 10.6 Na Carbonate 23 Polymer A 0.3 Dequest 2066 0.4Sokalan CP5 0.9 Savinase 16L 0.7 Lipolase 0.1 Minors 0.4 Water/salts Upto 100%

EXAMPLE 6 Detergent Granulate Prepared by Non-Spray Drying Method:

[0238] Component % w/w Na PAS 13.5 Dobanol 25-7 2.5 STPP 45.3 NaCarbonate 4 Polymer A 0.28 Na Silicate 10.1 Minors 1.5 Water Up to 100%

EXAMPLE 7 Isotropic Laundry Liquid

[0239] Component % w/w Na Citrate 10.7 Propylene Glycol 7.5 EthyleneGlycol 4.5 Borax 3 Savinase 16L 0.3 Lipolase 0.1 Polymer A 0.25Monoethanolamine 0.5 Coco fatty acid 1.7 NaOH (50%) 2.2 LAS 10.3 Dobanol25-7 6.3 LES 7.6 Minors 1.3 (adjust pH to 7 white NaOH) Water Up to 100%

EXAMPLE 8 Structured Laundry Liquids

[0240] Component % w/w LAS 16.5 Dobanol 25-7 9 Oleic acid (Priolene(6907)) 4.5 Zeolite 15 KOH, neutralisation of acids and pH to 8.5 Citricacid 8.2 Defloculating Polymer 1 Protease 0.38 Lipolase 0.2 Polymer A0.15 Minors 0.4 Water Up to 100%

1. A substituted polysaccharide comprising β₁₋₄ linkages havingcovalently bonded on the polysaccharide moiety thereof, at least onedeposition enhancing group which undergoes a chemical change in water ata use temperature to increase the affinity of the substitutedpolysaccharide to a substrate, the substituted polysaccharide furthercomprising one or more independently selected silicone chains.
 2. Asubstituted polysaccharide according to claim 1, wherein the averagedegree of substitution of the silicone chain(s) is from 0.001 to 0.5,preferably from 0.01 to 0.5, more preferably from 0.01 to 0.1, even morepreferably from 0.01 to 0.05.
 3. A composition as claimed in claim 1 or2 wherein the substituted polysaccharide comprises only β1-4 linkages.4. A composition as claimed in claim 1 or 2 claims wherein thesubstituted polysaccharide comprises additional linkages.
 5. Acomposition as claimed in claim 4 wherein the substituted polysaccharidecomprises β1-4 and β1-3 linkages.
 6. A composition as claimed in claim 5wherein the weight ratio of β1-3 and β1-4 linkages is from 1:100 to 1:2.7. A substituted polysaccharide according to any of the precedingclaims, wherein the silicone chain(s) is or are independently selectedfrom those of formula:

wherein L is absent or is a linking group and one or two of substituentsG¹-G³ is a methyl group, the remainder being selected from groups offormula

the —Si(CH₃)₂O— groups and the —Si(CH₃O)(G⁴)- groups being arranged inrandom or block fashion, but preferably random. wherein n is from 5 to1000, preferably from 10 to 200 and m is from 0 to 100, preferably from0 to 20, for example from 1 to
 20. G⁴ is selected from groups offormula: —(CH₂)_(p)—CH₃, where p is from 1 to 18—(CH₂)_(q)—NH—(CH₂)_(r),—NH₂ where q and r are independently from 1 to 3—(CH₂)_(s)—NH₂, where s is from 1 to 3

 where t is from 1 to 3 —(CH₂)_(u)—COOH, where u is from 1 to 10,

 where v is from 1 to 10, and —(CH₂ CH₂O)_(w)—(CH₂)_(x)H, where w isfrom 1 to 150, preferably from 10 to 20 and x is from 0 to 10; and G⁵ isindependently selected from hydrogen, groups defined above for G⁴, —OH,—CH₃ and —C(CH₃)₃
 8. A substituted polysaccharide according to claim 7,where L is selected from amide linkages, ester linkages, ether linkages,urethane linkages, triazine linkages, carbonate linkages, amine linkagesand ester-alkylene linkages.
 9. A substituted polysaccharide accordingto any preceding claim, wherein the chemical change is hydrolysis,perhydrolysis or bond-cleavage, optionally catalysed by an enzyme oranother catalyst.
 10. A substituted polysaccharide according to anypreceding claim, wherein the group(s) which undergo the chemical changecomprise one or more groups attached via an ester linkage to thepolysaccharide.
 11. A substituted polysaccharide according to anypreceding claim, having the general formula (1):—

(optional β₁₋₃ linkages and/or other linkages and/or other groups beingpermitted in the formula (I)) wherein at least one or more —OR groups ofthe polymer are independently substituted or replaced by silicone chainsand at least one or more R groups are independently selected from groupsof formulae:

wherein each R¹ is independently selected from C₁₋₂₀ (preferably C₁₋₆)alkyl, C₂₋₂₀ (preferably C₂₋₆) alkenyl (e.g. vinyl) and C₅₋₇ aryl (e.g.phenyl) any of which is optionally substituted by one or moresubstituents independently selected from C₁₋₄ alkyl, C-₁₂ (preferablyC₁₋₄) alkoxy, hydroxyl, vinyl and phenyl groups; each R² isindependently selected from hydrogen and groups R¹ as hereinbeforedefined; R³ is a bond or is selected from C₁₋₄ alkylene, C₂₋₄ alkenyleneand C₅₋₇arylene (e.g. phenylene) groups, the carbon atoms in any ofthese being optionally substituted by one or more substituentsindependently selected from C₁₋₁₂ (preferably C₁₋₄) alkoxy, vinyl,hydroxyl, halo and amine groups; each R⁴ is independently selected fromhydrogen, counter cations such as alkali metal (preferably Na) or${\frac{1}{2}\quad {Ca}\quad {or}\quad \frac{1}{2}{Mg}},$

 and groups R¹ as hereinbefore defined; and groups R which together withthe oxygen atom forming the linkage to the respective saccharide ringforms an ester or hemi-ester group of a tricarboxylic- or higherpolycarboxylic- or other complex acid such as citric acid, an aminoacid, a synthetic amino acid analogue or a protein; any remaining Rgroups being selected from hydrogen and other substituents.
 12. Asubstituted polysaccharide according to claim 10 or 11 when dependent onclaim 8, wherein the ester-linked group(s) is/are selected fromcarboxylic acid esters.
 13. A substituted polyssaccharide according toany of claims 10 to 12, wherein the ester-linked group(s) is/areindependently selected from one or more of acetate, propanoate,trifluroacetate, 2-(2-hydroxy-1-oxopropoxy) propanoate, lactate,glycolate, pyruvate, crotonate, isovalerate, cinnamate, formate,salicylate, carbamate, methylcarbamate, benzoate, gluconate,methanesulphonate, toluene sulphonate, groups and hemiester groups offumaric, malonic, itaconic, oxalic, maleic, succinic, tartaric,aspartic, glutamic, and malic acids.
 14. A substituted polysaccharideaccording to any preceding claim, wherein the average degree ofsubstitution on the saccharide rings of the groups which undergo thechemical change is from 0.1 to 3, preferably from 0.1 to
 1. 15. Asubstituted polysaccharide according to any preceding claim, furthercomprising one or more other pendant groups which are neither siliconechains nor groups which undergo a chemical change to enhance substrateaffinity.
 16. A substituted polysaccharide according to claim 15,wherein the average degree of substitution of other pendant groups isfrom 0.01 to 0.5, preferably from 0.01 to 0.05.
 17. A method ofdepositing a silicone onto a substrate, the method comprising contactingin an aqueous solution, the substrate and a substituted polysaccharideas according to any preceding claim.
 18. A composition comprising asubstituted polysaccharide as according to any one of claims 1 to 16 andat least one further component.
 19. A composition according to claim 18,in which the further component comprises a surfactant.
 20. A compositionaccording to claims 18 or claim 19, comprising from 0.01% to 25%,preferably from 0.1% to 10%, more preferably from 0.5% to 3% by weightof the substituted polysaccharide according to any of claims 1-16. 21.Use of a composition according to any of claims 18 to 20 to enhance thesoftening benefit of the composition on a substrate.